Diffusion resistant lenticular element

ABSTRACT

A process of forming a diffusion resistant lenticular element: a) contacting at least one dye-donor element having a support having thereon a dye layer having an image dye in a binder having an infrared-absorbing material associated therewith, the image dye comprising a nonionic dye capable of being converted to a cationic dye with an acid, with a lenticular element having a support with a lenticular array thereon on the opposite side thereof; b) imagewise-heating the dye-donor element with a laser; c) transferring a dye image to the support of the lenticular element; d) contacting the dye image with an acidic mordanting layer; and e) heating the lenticular element to cause the nonionic dye to convert to a cationic dye which is mordanted in the acidic mordanting layer.

CROSS REFERENCE TO RELATED APPLICATIONS

Reference is made to commonly-assigned copending U.S. patent applicationSer. No. 09/404,093, filed of even date herewith, Docket 79878HECentitled “Process for Obtaining a Diffusion Resistant LenticularElement”, of Tutt et al; and copending U.S. patent application Ser. No.09/404,062, filed of even date herewith, Docket 79772HEC entitled“Diffusion Resistant Lenticular Element”, of Tutt et al; the teachingsof which are incorporated herein by reference.

FIELD OF THE INVENTION

This invention relates to the laser printing of stereoscopic, multipleimages or motion images which will be used in conjunction with alenticular element.

BACKGROUND OF THE INVENTION

Lenticular arrays or overlays are a known means to give images theappearance of depth or motion. A lenticular image is created using atransparent upper layer having narrow parallel lenticules (halfcylindrical lenses) on the outer surface and an image containingsubstrate or lower layer which projects images through the lenticules.The two layers form a lenticular system wherein each image isselectively visible as a function of the angle from which the system isviewed. A depth image is a composite picture made by bringing togetherinto a single composition a number of different parts of a scene viewedfrom different angles. When the lenticules are vertically oriented, eacheye of a viewer will see different elements and the viewer willinterpret the net result as depth of field. The viewer may also move hishead with respect to the image thereby observing other views with eacheye and enhancing the sense of depth. Each lenticule is associated witha plurality of image lines or an image line set and the viewer issupposed to see only one image line (or view slice) of each set witheach eye for each lenticule. It is imperative that the line image setsbe registered accurately with the lenticules, so that the proper pictureis formed when the assembly is viewed.

This process can be used to generate a three-dimensional effect at aproper viewing distance or multiple images by viewing from differentangles. When the lenticules are oriented horizontally, each eye receivesthe same image. In this case, the multiple images upon moving thelenticular can be used to generate the illusion of motion. For whicheverorientation the lenticules are oriented, each of the viewed images isgenerated by lines from an image which has been interlaced substantiallyat the frequency of the lenticular array, number of lenticules perlength and with the desired number of images.

One method of recording of linear images on a lenticular recordingmaterial is accomplished with a stereoscopic image recording apparatus(hereunder referred to simply as “a recording apparatus”) that reliesupon optical exposure (printing). With this recording apparatus,original transmission images are projected from a light source. Thelight transmitted through the original images passes through theprojection lenses of the recording apparatus to be focused on thelenticular recording material via a lenticular sheet. The originalimages are thereby exposed as linear images.

Another method of image recording uses scanning exposure which requirescomparatively simple optics and yet has great flexibility in adapting tovarious image-processing operations and to alterations in thespecifications of the lenticular sheet.

In the article entitled “Development of Motion Image Printer”, by H.Akahori et al., IS&T 50th Annual Conference Proceedings, page 305, thereis a disclosure of a printer for printing stereoscopic images using athermal head and thermal dye transfer in registration with thelenticular material. The receiver sheet must be heated to achieve thenecessary stability for registration of the images with the lenticularmaterial. The resolution is six images on 100 DPI lenticular materialwith a 300 DPI thermal head. However, there is a problem with thismethod in that low resolution images are obtained, since heattransferred from the resistive head “spreads” through the support duringprinting.

EP 0 596 629A2 and EP 0 659 026A2 disclose a method and apparatus fordirectly printing on lenticular supports using lasers. This methodgenerates an image in contact with the lenticular material. There is aproblem with this method, however, in that the dyes can continue tomigrate after transfer, resulting in unacceptable image ghosting(adjacent views bleeding through).

An object of this invention is to generate high resolution lenticularimages which are resistant to thermal dye diffusion. It is anotherobject of this invention to generate images efficiently with highabrasion resistance.

SUMMARY OF THE INVENTION

These and other objects are achieved in accordance with this inventionwhich relates to a diffusion resistant lenticular element comprising asupport having a lenticular array thereon, the element having thereon anacidic mordanting layer containing a laser-induced, cationic dye image,the mordanting layer being on the side of the support which does notcontain the lenticular array.

Another embodiment of the invention relates to a process of forming adiffusion resistant lenticular element comprising:

a) contacting at least one dye-donor element comprising a support havingthereon a dye layer comprising an image dye in a binder having aninfrared-absorbing material associated therewith, the image dyecomprising a nonionic dye capable of being converted to a cationic dyeby means of an acid, with a lenticular element comprising a supporthaving a lenticular array thereon on the opposite side thereof;

b) imagewise-heating the dye-donor element by means of a laser;

c) transferring a dye image to the support of the lenticular element;

d) contacting the dye image with an acidic mordanting layer; and

e) heating the element to cause the nonionic dye to convert to acationic dye which is mordanted in the acidic mordanting layer.

By use of the invention, a high resolution lenticular image is generatedefficiently which is resistant to thermal dye diffusion and has a highabrasion resistance.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As noted above, dyes useful in the invention are nonionic dyes capableof being converted to cationic dyes by means of an acid. A cationic dyediffuses much less readily than a nonionic dye due to electrostaticforces retarding movement. An example of an nonionic dye which convertsto a cationic dye in the presence of an acid is the following (Since thechromophore is involved in the reaction, there is a color changeindicating the state of the dye molecule):

Examples of such dyes which may be used in the invention are of manyclasses. For example, the dye may be a deprotonated cationic dye whichis capable of being reprotonated to a cationic dye having an N—H groupwhich is part of a conjugated system. Additional examples of such dyesare disclosed in U.S. Pat. No. 5,523,274, the disclosure of which ishereby incorporated by reference, and include the following:

Another class of dyes useful in the invention is a pendant basic dyecapable of being protonated to a cationic dye, as disclosed in U.S. Pat.Nos. 5,512,532, 5,744,422, and 5,804,531, the disclosures of which arehereby incorporated by reference. An example of a pendant basic dyewhich converts to a cationic dye in the presence of an acid is thefollowing:

Additional examples of such dyes include the following:

Another class of dyes useful in the invention is a lactone leuco dye 10capable of being protonated to a cationic dye, as disclosed in U.S. Pat.No. 5,830,823 and copending U.S. Ser. No. 08/996,388, the disclosures ofwhich are hereby incorporated by reference. An example of a lactoneleuco dye which converts to a cationic dye in the presence of an acid isthe following:

An additional example of such dyes includes the following:

Another class of dyes useful in the invention is a carbinol dye capableof being protonated to a cationic dye, as disclosed in U.S. Pat. No.5,804,531, the disclosure of which is hereby incorporated by reference.An example of a carbinol dye which converts to a cationic dye in thepresence of an acid is the following:

The mordanting layer useful in the invention is acidic, which may be theresult of adding an acid to a polymer or using an acidic polymer. In apreferred embodiment of the invention, an acidic polymer is used such asdescribed in U.S. Pat. No. 5,523,274, the disclosure of which is herebyincorporated by reference. Examples of such polymers includecondensation polymers such as polyesters, polyurethanes, polycarbonates,etc.; addition polymers such as polystyrenes, vinyl polymers, etc.;block copolymers containing large segments of more than one type ofpolymer covalently linked together; provided such polymeric materialcontains acid groups as part of the polymer chain. In a preferredembodiment of the invention, the mordanting layer comprises an acrylicpolymer, a styrene polymer or a phenolic resin.

The dyes of the dye-donor element used in the invention can optionallybe dispersed in a polymeric binder such as a cellulose derivative, e.g.,cellulose acetate hydrogen phthalate, cellulose acetate, celluloseacetate propionate, cellulose acetate butyrate, cellulose triacetate orany of the materials described in U.S. Pat. No. 4,700,207; polyvinylbutyrate; copolymers of maleic anhydride with vinyl ethers such asmethyl vinyl ether; polycyanoacrylates; a polycarbonate; poly(vinylacetate); poly(styrene-co-acrylonitrile); a polysulfone or apoly(phenylene oxide), gelatin, etc. The binder may be used at acoverage of from about 0.1. to about 5 g/m².

Any material can be used as the support for the lenticular array of theinvention provided it is dimensionally stable. Such materials includepolyesters such as poly(ethylene terephthalate); polyamides;polycarbonates; cellulose esters such as cellulose acetate; fluorinepolymers such as poly(vinylidene fluoride) orpoly(tetrafluoroethylene-co-hexafluoropropylene); polyethers such aspolyoxymethylene; polyacetals; polyolefins such as polystyrene,polyethylene, polypropylene or methylpentene polymers; and polyimidessuch as polyimide-amides and polyether-imides. The support generally hasa thickness of from about 50 to about 5000 μm. While the lenticulararray may be provided on a separate support, generally the support andthe array are in one integral element.

Infrared-absorbing materials which may be used in the invention includecarbon black, cyanine infrared-absorbing dyes as described in U.S. Pat.No. 4,973,572, or other materials as described in the following U.S.Pat. Nos. 4,948,777; 4,950,640; 4,950,639; 4,948,776; 4,948,778;4,942,141; 4,952,552; 5,036,040; and 4,912,083, the disclosures of whichare hereby incorporated by reference.

A laser is used to transfer dye from the dye-donor element used in theinvention. It is preferred to use a diode laser since it offerssubstantial advantages in terms of its small size, low cost, stability,reliability, ruggedness, and ease of modulation

Lasers which can be used to transfer dye from dye-donors employed in theinvention are available commercially. There can be employed, forexample, Laser Model SDL-2420-H2 from Spectra Diode Labs, or Laser ModelSLD 304 V/W from Sony Corp.

A thermal printer which uses the laser described above to form an imageon a thermal print medium is described and claimed in U.S. Pat. No.5,268,708, the disclosure of which is hereby incorporated by reference.

Spacer beads may be employed in a separate layer over the dye layer ofthe dye-donor element in the above-described laser process in order toseparate the donor from the receiver during dye transfer, therebyincreasing the uniformity and density of the transferred image. Thatinvention is more fully described in U.S. Pat. No. 4,772,582, thedisclosure of which is hereby incorporated by reference. Alternatively,spacer beads may be employed in the receiving layer of the receiver asdescribed in U.S. Pat. No. 4,876,235, the disclosure of which is herebyincorporated by reference. The spacer beads may be coated with apolymeric binder if desired.

As noted above, in the process of the invention, the lenticular elementwith the transferred dye is heated to cause the nonionic dye to convertto a cationic dye which is mordanted in the adhesive layer. This heatingmay be accomplished, for example by passing the element between a pairof heated rollers. Other methods of heating could also be used such asusing a heated platen, use of pressure and heat, external heating, etc.Mechanical adhesion may be used to maintain registration after heatingand mordanting if sufficient adhesion does not occur between the acidicmordanting layer and the lenticular array element. The mechanicaladhesion, for example, can be in the form of clamps, registration pinsor a frame.

The following examples are provided to illustrate the invention.

EXAMPLES Example 1

The following control dyes were employed which contain dialkylarylaminesand quinone imines which are not readily protonated except under extremeacidic conditions:

Control Dye Donor Element 1

The donor element was coated with a laydown of 0.22 g/m² carbon black,Cabot Black Pearls 700 ® (Cabot Corp.), 0.54 g/m² polyvinylbutyral,(Butvar ®76, Monsanto Co.), 0.01 g/m² Fluorad FC 431 ® surfactant (3MCo.), 0.02 g/m² crosslinked polydivinylbenzene beads, 5.4 μm, and 0.54g/m2 of Control Dye 1 from methyl isobutyl ketone on a 104 μm thickpoly(ethylene terephthalate) support.

Control Dye Donor Elements 2-3

These donor elements were prepared the same as Control Dye Donor Element1 except that Control Dye 2 and Control Dye 3 were used instead ofControl Dye 1.

Elements 1-11 Used In The Invention

These donor elements were prepared the same as Control Dye Donor Element1 except that Dyes 1-11were used instead of Control Dye 1.

Polymeric Acidic Mordanting Layer Used In The Invention

A 0.31 mm cast film of the ammonia salt of poly{isophthalicacid-co-5-sulfoisophthalic acid (90:10 molar ratio)-diethylene glycol(100 molar ratio)}, MW=20,000 (ammonium salt of AQ29D, Eastman ChemicalCo.) and 0.02 g/m² Dispex N-40® surfactant (Ciba Specialty Chemicals)was used.

Protective Support with Acidic Polymeric Mordanting Layer

A 36 μm thick poly(ethylene terephthalate) support was coated with anaqueous coating of 3.22 g/m² of the ammonia salt of poly{isophthalicacid-co-5-sulfoisophthalic acid (90:10 molar ratio)-diethylene glycol(100 molar ratio)}, MW=20,000 (ammonium salt of AQ29D, Eastman ChemicalCo.) and 0.02 g/m² Dispex N-40 ® surfactant (Ciba Specialty Chemicals).

Lenticular Array

A polycarbonate lenticular material which consisted of cylindricallenses on one face and a flat rear face was used. This lenticularmaterial had a pitch of 1.973 lines/mm and a thickness of 1.27 mm. Thelens curvature was such that focus was on the rear of the lenticularmaterial.

Printing

A dye-donor element was placed dye side to flat rear side of thelenticular array and vacuum was applied to hold the donor to the array.Printing was accomplished using an SDL 23-S9781 1 watt c-mount laserdiode (Spectra Diode Labs, Inc.). Approximately 700 mw was delivered tothe element in a spot approximately 13 μm by 80 μm using the techniqueof beam folding as disclosed in copending application U.S. Ser. No.09/175,735 of Kessler, filed Oct. 20, 1998. Scanning of the spot wasaccomplished using a galvanometer with the beam oriented with the longaxis parallel to the scan direction as described in the copendingapplication U.S. Ser. No. 09/128,077, of Kessler et al., filed Aug. 3,1998. Dwell time was approximately 9 microseconds, except for dyes 8-11which ere at 19 microseconds.

A target image consisting of lines spaced at multiples of 11 μm waswritten on to the back of the donor causing the donor dye to betransferred to the lenticular material. Thus, lines are spaced at 11,21, 32 and 42 μm, creating gaps between adjacent lines. The lines werewritten such that the donor lines were parallel to the lenticules. Thisspacing was such that the proper viewing of a flat field image was about30 cm. By holding the card at another distance, either nearer orfarther, the individual lines and spacings could be observed via a Moiréeffect.

Mordanting of the dyes and lamination of the acidic mordanting layerwith and without a protective support was accomplished by passing thelenticular element and the acidic mordanting layer through a laminatorwith the acidic mordanting layer in contact with the flat side of thelenticular array. The acidic mordanting layer without a protectivesupport was laminated against Teflon®. The lamination was conducted witha feed rate of 0.36 cm/sec at a temperature of 133° C. The laminator wasa modified GMP Co. LTD (Kyoungki-Do, Korea) laminator modelPassport-175LSI. The modification was to adjust the gap thickness toaccommodate the 1270 μm lenticular material.

The color of the printed lines was observed before and after laminationand are recorded in Table 1 below. Some of the dyes change color sinceprotonation alters the chromophore. This is an indication thatmordanting has taken place in those classes of dyes. Pendent amine Dyes5-7 are examples of protonation taking place in the pendent group, andnot in the chromophore.

The 36 μm poly(ethylene terephthalate) protective support providesexcellent abrasion resistance. Scraping with a paper clip afforded nodye movement or scratching of the dye image.

All spacings between written lines could be clearly seen afterlamination in all lenticular images generated from the different donorelements prior to thermal keeping. For a thermal keeping test, thelaminated cards were placed in an oven at 160° F. for 6 hours and thespacings between lines observed as discussed previously. For a highresolution lenticular element, the gaps should not be filled in.Modulation is a measure of how much the gaps are filled in. A strongmodulation is an indication of little thermal dye diffusion. Weakmodulation indicates significant thermal dye diffusion filling in a gapand is undesirable.

A gap of 11 μm between written lines is designated a one line spacing. Agap of 22 μm between written lines is designated a two line spacing. Agap of 33 μm between written lines is designated a three line spacing.The following diffusion number rating system was employed (lower numbersare desirable since this is an indication of the gap not be filled indue to increased thermal dye diffusion stability):

Diffusion Number Rating

1 Strong modulation of 1 line spacing (11 μm )

2 Weak modulation of 1 line spacing

3 No modulation of 1 line spacing, strong modulation of 2 line spacing(21 μm)

4 Weak modulation of 2 line spacing

5 No modulation of 2 line spacing, strong modulation of 3 line spacing(32 μm)

6 Weak modulation of 3 line spacing

7 No modulation of 3 line spacing, modulation of 4 line spacing (42 μm)

The following results were obtained:

TABLE Element Lamination Con- With Diffusion Number Color tainingProtective Before After Before After Dye Support Heating HeatingLamination Lamination Control 1 Yes 1 5 Cyan Cyan Control 2 Yes 1 7Magenta Magenta Control 3 Yes 1 6 Yellow Yellow 1 Yes 1 3 Magenta Cyan 2Yes 1 3 V. Pale Yellow Yellow 3 Yes 1 3 Orange Magenta 4 Yes 1 3 YellowOrange 5 Yes 1 3 Cyan Cyan 6 Yes 1 2 Magenta Magenta 6 No 1 3 MagentaMagenta 7 Yes 1 1 Yellow Yellow 8 Yes 1 3 Colorless Black 9 Yes 1 1Colorless Blue 10  Yes 1 1 Orange Magenta 11  Yes 1 1 Pale Yellow Yellow

The above results show that the dyes used in the invention had amobility than the control dyes as evidenced by having a lower diffusion

The invention has been described in detail with particular referencepreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:
 1. A process of forming a diffusion resistantlenticular element comprising: a) contacting at least one dye-donorclement comprising a support having thereon a dye layer comprising animage dye in a binder having an infrared-absorbing material associatedtherewith, said image dye comprising a nonionic dye capable of beingconverted to a cationic dye by means of an acid, with a lenticularelement comprising a support having a lenticular array thereon on theopposite side thereof; b) imagewise-heating said dye-donor element bymeans of a laser; c) transferring a dye image to said support of saidlenticular element; d) contacting said dye image with an acidicmordanting layer; and e) heating said lenticular element to cause saidnonionic dye to convert to a cationic dye which is mordanted in saidacidic mordanting layer.
 2. The process of claim 1 wherein saidmordanting layer comprises an acidic polymer.
 3. The process of claim 1wherein said cationic dye is a protonated cationic dye having a N—Hgroup which is part of a conjugated system.
 4. The process of claim 1wherein said cationic dye is a protonated pendant basic dye.
 5. Theprocess of claim 1 wherein said cationic dye is a protonated lactoneleuco dye.
 6. The process of claim 1 wherein said cationic dye is aprotonated carbinol dye.